Preparation of titanium compounds



Patented Jan. 26, 1937 UNITED STATES- PATENT OFFICE Crundall, Manchester, Peter Spence & Sons,

England No Drawing. No. 709,296.

England, assignors to Limited, Manchester,

Application February 1, 1934, Serial In Great Britain February 7, 1933 8 Claims. (Cl. 23-105) The employment of titanium compounds in the arts for dyeing, mordanting, tanning etc. in the treatment of textiles, leather and the like and for other purposes is known and compounds of titanium such as the titanium salts of mineral acids, e. g., sulphuric acid, of organic acids, e. g., oxalic acid, lactic acid, or the double salts of titanium and an alkali metal, e. g., sodium, with mineral acids, e. g., sulphuric acid, in the form of the compound TlSO4NazSO4 aq. or with organic acids, e. g.,oxalic acid in the form of titanium potassium oxalate, or mixtures of mineral acid titanium salts such as the double sulphate TiOSO4Na2SO4 aq. withv organic acids and/or their'salts e. g., oxalic acid, sodium binoxalate, have been used for such purposes. Of these, the. products free from the mineral acids,

sulphuric acid and hydrochloric acid, have proved to be generally the more stable in use, i. e. to

have little or no tendency to precipitate insoluble titanium compounds on dilution and/or on heating. acid, in the form e. g., of sulphuric acid, on the other hand, may usually be made more economically, but the total acid present after allowing for other bases than titanium is in excess of that required for a normal salt and such excess of acid part or all of whichmay be present as mineral acid, e. g., sulphuric acid, is, for some purposes, unsuitable and under some conditions of usage may have a deleterious action on' the material being treated.

We have now found that soluble compounds or mixtures containing titanium in association with phosphoric acid and/or suitable phosphates and suitable organic acids, e. g., oxalic acid, tartaric acid and/or suitablesalts of organic acids, e.g., sodium binoxalate, can be prepared and that the solutions obtainable therefrom are especially suitable for use in dyeing, mordanting, tanning and for othenpurposes, are more economical to produce than compounds such as titanium p0.- tassium oxalate, may possessyery high stability even when the organic acid present amounts to only about, e. g., 1% mol. 'or less of divalent acid tendering ac-'- tionon materials dyed, mordanted or otherwise In addition, we find that such solutions dye'or mordant more evenly -than those per mol. T102 and have minimum treated therewith.

hitherto used for the purpose and may, owing to the presence of the phosphoricacid, give inovel effects as mordants, e. g., in completeness of precipitation, in tone, brightness etc., in the formation of colour lakes, in tanning. etc, We ilnd and sodium binoxalate as we The compounds containing mineral are usually incompletely stable unless that such soluble compounds or mixtures may be prepared by combining the desired ingredients in diflerent ways. We may, for example, mix

together under suitable conditions of concentration and temperature, titanium phosphate, such as e. g., the basic titanium phosphates described in British Patents Nos. 261,051 and 290,683 and particularly basic phosphate precipitated from solutions containing not very high proportion of free acid e. g., from solutions containing about- 2 mols of acid expressed as P04 per mol. T102,

find that such titanium phosphates, although they are very dimcultly soluble in mineral acid solutions, are read- 11y soluble in the presence of suitable organic salts and their acid salts, such as e. g. oxalic acid or sodium binoxalate; or we may similarly mix readily acid soluble hydrated titanium oxide, a suitable organic acid and/orsalt of an organic acid, e. g., oxalic acid or sodium binoxalate, and phosphoric acid and/or a suitable phosphate, e. g., sodium phosphate, or we may similarly mix titanium salts of organic acids, e. g., basic titanium oxalate, phosphoric acid and/or a suitable phosphate, and any desired amount of a. suitable organic acid and/or salt of an organic acid; e. g., oxalic acid and/or sodium binoxalate, and our invention consists in such preparation and use of such soluble compounds and mixtures containing titanium in association with phosphoric acid and/or a suitable phosphate and suitable organic acids and/or their sal s.

. In carrying our invention into'eiiect we may intimately 'mix together by known means the minimum amount of evaporation or not any is subsequently required. Thus, for'example, we may intimately mix together by known means a quantity of a basic titanium phosphate paste prepared by the methods described in British Patents Nos. 261,051 and 290,683 and which may suitably have a phosphoric acid content of about 0.2 mol. P205 to 1 mol. TiOz with a quantity of sodium binoxalate equivalent toabout 1 mol. on the TiOz present, heat until solution is efi'ected and, if necessary, evaporate the resultant solugether by known tion by known means until it yields a solid product which is readily soluble and stable in water and which may contain, e. .g., by weight of Ti02, or. we may intimately mix together by known means a quantity of basic titanium oxalate containing say 0.4 mol. C203 per mol. of T102 with oxalic acid sufiicient to bring the total C203 content to about 1 to 1 mols per mol. of 'IiOz and the desired quantity of sodium phosphate, e. g. equivalent to about 0.2 to 0.3 mol. P205 per mol. Ti02, heat until solution is effected and treat as before, or we may intimately mix tomeans a quantity of orthotitanic hydrate with the equivalent of about 1 to 1% mols of sodium binoxalate and the desired quantity of phosphoric acid, heat until solution is effected and treat as before.

To bring about the desired combinations we may use organic acids alone or their salts with suitable metals, e. g. their sodium salts, or mixtures of the acids and their salts in any desired proportions, provided suflicient free acid is present to keep the titanium in solution. Other suitable organic acids, such as e. g. lactic acid, tartaric acid, and their salts may be employed but oxalic acid may offer advantages in cost.

If desired, we may subsequently mix the dry product obtained as described with additional organic acid and/or a suitable salt of an organic acid e. g. oxalic acid or sodium binoxalate.

What we claim as our invention and desire to secure by letters Patent is:-

1. The process for producing a soluble titanium material suitable for dyeing, mordanting, tanning, lake manufacture and the like which process comprises mixing together materials containing titanium, phosphoric acid and an oxalic acid, the oxalic acid being present in amounts not less than one mol. of acid per mol. of T102, and heating the mixture to effect solution.

2. The process for producing a soluble titanium material suitable for dyeing, mordanting, tanning, lake manufacture and the like which process comprises mixing together titanium phosphate having an acid content of about 0.2 mol. P205 to 1 mol. Ti02, and sodium binoxalate in an amount equivalent to about 1 mol. per mol. of T102, and heating the mixture to effect solution.

3. The process for producing a soluble titanium material suitable for dyeing, mordanting, tanning, lake manufacture and the like which process comprises mixing together basic titanium oxalate containing about 0.4 mol. C203 per mol. of T102, oxalic acid in an amount sufficient to bring the total C203 content to about 1 to 1% mols. per mol. of Ti02 and sodium phosphate having an acid content of from 0.2 to 0.3 mol. P205 per mol. of T102, and heating the mixture to effect solution.

4. The process for producing a soluble titanium material suitable for dyeing, mordanting, tanning, lake manufacture and the like which process comprises mixing together orthotitanic hydrate, sodium binoxalate in amounts equivalent to about 1 to 1 mols. per mol. Ti02 and phosphoric acid, and heating the mixture to effect solution.

5. A material suitable for dyeing, mordanting, tanning, lake manufacture and the like which comprises the resultant product of a solution of materials containing titanium, phosphoric acid and oxalic acid, the oxalic acid being present in an amount of not less than 1 mol. per mol. of

TiO2.

6. A material suitable for dyeing, mordanting, tanning, lake manufacture and the like which comprises the resultant product of a solution of titanium phosphate having an acid content of about 0.2 mol. P205 per mol. Ti02, and sodium binoxalate in an amount equivalent to about 1 mol. per mol. of T102.

'7. A material suitable for dyeing, mordanting, tanning, lake manufacture and the like which comprises the resultant product of a solution of basic titanium oxalate containing about 0.4 mol. C203 per mol. T102, oxalic acid in an amount sufficient to bring the C202 content to about 1 to 1% mols. per mol. H02, and sodium phosphate having an acid content of from 0.2 to 0.3 mol. P205 per mol. T102.

8. A material suitable for dyeing, mordanting, tanning, lake manufacture and the like which comprises the resultant product of a solution of orthotitanic hydrate, sodium binoxalate in an amount equivalent to about 1 to 1 mols. per mol. Ti02, and phosphoric acid.

HOWARD SPENCE.

SYDNEY FRANCIS WILLIAM CRUNDALL. 

